In this work, 3D structuration of LTCC (low-temperature co-fired ceramic) for microfluidics was studied, using two novel sacrificial carbon paste compositions. These pastes are based on graphite with a water-soluble vehicle consisting of polyvinylpyrrolidone binder (PVP) dissolved in propylene glycol (PG), which is not aggressive to green LTCC material. Both examined pastes differ slightly in binder content and added plasticizer, glycerol (G) or trimethylolpropane (TMP). The thermal properties of the sacrificial carbon pastes have been examined using combined thermo-gravimetric analysis (TGA), differential thermal analysis (DTA) and differential thermo-gravimetry (DTG). The sacrificial carbon pastes have been applied to the fabrication of membranes and microchannels in LTCC substrate. A comparison of the obtained features has been made using X-ray tomography and optical profile measurements. Moreover, changes in the composition of the fired LTCC material after co-firing have been studied using X-ray photoelectron spectroscopy (XPS) and surface wettability measurements.